Negative active material composition for a rechargeable lithium battery, a negative electrode for a rechargeable lithium battery, and a rechargeable lithium battery including same

ABSTRACT

Negative active material compositions for rechargeable lithium batteries, negative electrodes for rechargeable lithium batteries, and rechargeable lithium batteries using the negative active material compositions are provided. The negative active material composition includes a negative active material, a polyimide precursor compound, and a highly flexible polymer. The negative active material composition prevents the electrode substrate from bending, thereby improving the capacity and cycle-life characteristics of the battery.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean PatentApplication No. 10-2006-0117904 filed in the Korean IntellectualProperty Office on Nov. 27, 2006, the entire content of which isincorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to negative active material compositionsfor rechargeable lithium batteries, to negative electrodes forrechargeable lithium batteries, and to rechargeable lithium batteriesincluding the same.

2. Description of the Related Art

Lithium rechargeable batteries use materials that reversibly intercalateor deintercalate lithium ions during charge and discharge reactions forboth positive and negative active materials. Lithium rechargeablebatteries also use organic electrolytes or polymer electrolytes betweenthe positive electrodes and the negative electrodes.

Lithium rechargeable batteries generate electrical energy from oxidationand reduction of lithium ions during intercalation and deintercalationat the positive and negative electrodes. Such rechargeable lithiumbatteries have high cell voltages and large energy densities due to thehigh standard electrochemical potential of lithium ions.

Lithium-transition element oxides have been used as the positive activematerial of rechargeable lithium batteries. Crystalline or amorphouscarbon or carbon composites have been used as the negative activematerial.

Each of the positive and negative active materials is coated on acurrent collector at an appropriate thickness and length to fabricatepositive and negative electrodes. Alternatively, each of the positiveand negative active materials is formed into a film to fabricatepositive and negative electrodes. The positive and negative electrodesand a separator positioned between the positive and negative electrodesare then wound or stacked to fabricate an electrode assembly. Theelectrode assembly is placed in a can or other case and an electrolytesolution is injected therein to fabricate a prismatic rechargeablebattery.

Generally, the negative electrode for a rechargeable lithium battery isfabricated by mixing a negative active material, a binder, andoptionally a conductive agent to prepare a negative active materialcomposition, and coating the negative active material composition on acurrent collector to form a negative electrode.

Polyimide has good adhesion characteristics and shape stability at hightemperatures, and therefore can be used as the binder for the negativeelectrode of a rechargeable lithium battery requiring stability at hightemperatures. Polyimide is not used itself, but rather a precursor ofpolyimide is used in the negative active material composition. Polyamicacid (which is a precursor of polyimide) is converted into polyimideduring drying of the negative electrode preparation. The conversionreaction, which is a dehydration reaction, causes shrinkage of thepolyimide, resulting in bending of the negative electrode. In addition,the polyimide is rigid.

SUMMARY OF THE INVENTION

In one embodiment of the present invention, a negative active materialcomposition for a rechargeable lithium battery improves capacity andcycle-life by inhibiting electrode shrinkage.

In another embodiment of the present invention, a negative electrode isfabricated using the negative active material composition for arechargeable lithium battery.

In yet another embodiment of the present invention, a rechargeablelithium battery includes the negative electrode.

According to one embodiment of the present invention, a negative activematerial composition for a rechargeable lithium battery includes anegative active material, a polyimide precursor compound, and a highlyflexible polymer.

The polyimide precursor compound may be a compound produced by acondensation reaction between a first monomer and a second monomer. Thefirst monomer may be selected from compounds represented by Formulae 1to 4, and the second monomer may be selected from compounds representedby Formulae 5 to 9.

In Formulae 1 through 9, each of X₁ and X₂ is independently selectedfrom O, CO, SO₂, or S, and X₁ and X₂ may be the same or different. Eachof R₁ and R₂ is independently selected from H and alkyls, and R₁ and R₂may be the same or different. Each of R₃ and R₄ is independentlyselected from halogens, haloalkyls, alkyls, and H, and R₃ and R₄ may bethe same or different.

The highly flexible polymer has a glass transition temperature of about50° C. or less. According to one embodiment, the highly flexible polymerhas a glass transition temperature ranging from about −60° C. to about50° C.

The highly flexible polymer has a weight average molecular weightranging from about 10,000 to about 1,000,000. According to oneembodiment, the highly flexible polymer has a weight average molecularweight ranging from about 10,000 to 500,000.

The highly flexible polymer may be selected from compounds representedby Formulae 10 to 14, and combinations thereof.

In Formula 10, R₅ is an alkylene, and n ranges from 120 to 1000.

R₆—O_(n)   Formula 11

In Formula 11, R₆ is an alkylene, and n ranges from 250 to 25,000.

In Formula 12, R₇ to R₁₀ may be the same or different and each of R₇ toR₁₀ is independently selected from H and alkyls, and n ranges from 120to 12,000.

In Formula 13, R₁₁ and R₁₂ may be the same or different, and each of R₁₁and R₁₂ is independently selected from H and alkyls. X₃ and X₄ may bethe same or different and each of X₃ and X₄ is independently selectedfrom halogens, and n ranges from 150 to 10,000.

In Formula 14, R₁₃ and R₁₄ may be the same or different, and each of R₁₃and R₁₄ is independently selected from H and alkyls. X₅ to X₁₀ may bethe same or different, and each of X₅ to X₁₀ is independently selectedfrom halogens, a ranges from 120 to 900, and b ranges from 5100 to 5880.

According to another embodiment of the present invention, a negativeelectrode includes a current collector and a negative active materiallayer disposed on the current collector. The negative active materiallayer includes a negative active material, a polyimide precursorcompound, and a highly flexible polymer. The polyimide precursorcompound may be a compound produced by a condensation reaction between afirst monomer and a second monomer. The first monomer may be selectedfrom compounds represented by Formulae 1 to 4, and the second monomermay be selected from compounds represented by Formulae 5 to 9.

According to yet another embodiment of the present invention, arechargeable lithium battery includes the negative electrode, a positiveelectrode including a positive active material that is capable ofreversibly intercalating and deintercalating lithium ions, and anelectrolyte.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a schematic cross-sectional view of a prior art electrode ofa rechargeable lithium battery illustrating contraction of the negativeactive material layer;

FIG. 1B is a schematic cross-sectional view of the electrode of FIG. 1Ashowing the bending that occurs in the prior art electrode;

FIG. 2 is a schematic cross-sectional view of a rechargeable lithiumbattery according to one embodiment of the present invention;

FIG. 3 is a photograph of the negative electrode prepared according toExample 1;

FIG. 4 is a photograph of the negative electrode prepared according toExample 2;

FIG. 5 is a photograph of the negative electrode prepared according toExample 3;

FIG. 6 is a photograph of the negative electrode prepared according toComparative Example 1;

FIG. 7 is a photograph of the negative electrode prepared according toComparative Example 2; and

FIG. 8 is a photograph of the negative electrode prepared according toComparative Example 3.

DETAILED DESCRIPTION OF THE INVENTION

Polyimide is generally used as a binder for lithium alloy-basedbatteries and is rigid. Such polyimide is not used itself, but rather aprecursor of the polyimide is used in the negative active materialcomposition. Polyamic acid, which is a precursor of polyimide, isconverted into polyimide during drying of the negative electrodepreparation. The conversion reaction, which is a dehydration reaction,causes shrinkage of the polyimide, resulting in bending of the negativeelectrode.

The bending phenomenon of the negative electrode will be illustrated inmore detail.

In general, a negative electrode is prepared by mixing a polyimideprecursor compound, a negative active material, and optionally aconductive agent in an organic solvent to prepare a negative activematerial composition. The negative active material composition is coatedon a current collector and dried to form a negative active materiallayer.

The polyimide precursor compound undergoes a dehydration reaction inwhich water molecules are removed, and the precursor is therebyconverted into polyimide as shown in the following Reaction Scheme 1.

The dehydration reaction creates spaces due to the removal of the watermolecules, and the polyimide contracts by the same amount. Thecontraction of the polyimide may cause the negative active materiallayer to contract. As shown in FIG. 1A, the side III of the negativeactive material layer 1 that contacts the current collector 3 contractsto a different degree than the other side II. In other words, the sideIII of the negative active material layer 1 that contacts the currentcollector 3 contracts less than the other side II (i.e., an opensurface). The side III of the negative active material layer 1 thatcontacts the current collector 3 is less transformed because the currentcollector 3 has strong surface tension. This difference in the degree ofcontraction causes the negative electrode to bend as shown in FIG. 1B.

When the negative electrode is bent, it is extremely difficult to coatthe negative active material composition on both sides of the currentcollector because coating the side III after coating the side II is verydifficult. As a result, the amount of negative active material isdecreased, making it difficult to realize high capacity batteries.

In addition, when the bent part of the negative electrode is forciblystraightened, the negative electrode may form severe cracks on itssurface, deteriorating the electrochemical characteristics of theelectrode.

Furthermore, when a negative active material composition is coated insmall amounts on one side of the current collector to decrease bendingof the negative electrode, batteries formed therefrom may have decreasedcapacity.

In order to solve this problem, the present invention includes a binderprepared by blending a highly flexible polymer with polyimide. Inparticular, a negative active material composition for a rechargeablelithium battery according to one embodiment of the present inventioncontains enough of the highly flexible polymer to compensate for thevolume lost from contraction of the polyimide precursor compound due todehydration. As such, the binder may suppress bending of the negativeelectrode.

According to one embodiment of the present invention, a negative activematerial composition for a rechargeable lithium battery may include anegative active material, a polyimide precursor compound, and a highlyflexible polymer.

The negative active material may be selected from lithium metal, lithiumalloys, materials capable of reversibly forming lithium-containingcompounds, materials capable of reversibly intercalating anddeintercalating lithium ions, and combinations thereof. The lithiumalloy may be an alloy including lithium and another metal selected fromNa, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, Sn, and combinationsthereof.

Nonlimiting examples of suitable materials capable of reversibly forminglithium-containing compounds may include tin oxide (SnO, SnO₂), titaniumnitrate, silicon oxide (SiO, SiO_(x) where 0<x<2), silicon, andcombinations thereof.

The materials capable of reversibly intercalating and deintercalatinglithium may include carbon-based materials. The carbon-based materialsmay include amorphous carbon or crystalline carbon. The amorphous carbonmay be a soft carbon (carbon obtained by sintering at a lowtemperature), a hard carbon (carbon obtained by sintering at a hightemperature), mesophase pitch carbide, fired coke, and so on. Thecrystalline carbon may be non-shaped, or sheet, flake, spherical, orfiber shaped natural or artificial graphite.

The polyimide precursor compound includes a compound produced through acondensation reaction of a first monomer and a second monomer. The firstmonomer may be selected from compounds represented by Formulae 1 to 4,and the second monomer may be selected from compounds represented byFormulae 5 to 9.

In Formulae 1 through 9, X₁ and X₂ may be the same or different and eachof X₁ and X₂ is independently selected from O, CO, SO₂, or S. R₁ and R₂may be the same or different and each of R₁ and R₂ is independentlyselected from H and alkyls. R₃ and R₄ may be the same or different andeach of R₃ and R₄ is independently selected from halogens, haloalkyls,alkyls, and H. According to one embodiment, R₁ and R₂ are H, and R₃ andR₄ are either the same or independently selected from halogens,haloalkyls, alkyls, and H. According to another embodiment, R₁ and R₂are H, and R₃ and R₄ are haloalkyls. According to yet anotherembodiment, R₁ and R₂ are H, and R₃ and R₄ are fluoroalkyls.

In addition, the highly flexible polymer may have a glass transitiontemperature (Tg) of about room temperature or less. Specifically, thehighly flexible polymer has a glass transition temperature of about 50°C. or less. According to one embodiment, the highly flexible polymer hasa glass transition temperature ranging from about −60° C. to about 50°C. According to another embodiment, the highly flexible polymer has aglass transition temperature ranging from about −60° C. to about −30° C.

When the highly flexible polymer has a glass transition temperaturegreater than about 50° C., substrate flexibility deteriorates. On theother hand, when the highly flexible polymer has a glass transitiontemperature of at least about −60° C., substrate flexibility andadherence to the current collector improve.

The highly flexible polymer has a weight average molecular weightranging from about 10,000 to about 1,000,000. According to oneembodiment, the highly flexible polymer has a weight average molecularweight ranging from about 10,000 to about 500,000. When the highlyflexible polymer has a weight average molecular weight of less thanabout 10,000, the binder may dissolve or swell. On the other hand, whenthe highly flexible polymer has a weight average molecular weightgreater than about 1,000,000, it may be difficult to dissolve in asolvent.

The highly flexible polymer may be selected from compounds representedby Formulae 10 to 14 and combinations thereof. A nonlimiting, exemplarypolymer satisfying Formula 10 is polypropylene carbonate. Nonlimitingexemplary polymers satisfying Formula 11 include polyethylene oxide andpolypropylene oxide. A nonlimiting, exemplary polymer satisfying Formula12 is polyvinylacetate. A nonlimiting, exemplary polymer satisfyingFormula 13 is polyvinylidenefluoride. Nonlimiting, exemplary polymerssatisfying Formula 14 include polyvinylidenefluoride-hexafluoropropylenecopolymers. However, the highly flexible polymer is not limited theretoand may include any polymer having a low glass transition temperatureand satisfying the above conditions.

In Formula 10, R₅ is alkylene, and n ranges from 120 to 1000.

R₆—O_(n)   Formula 11

In Formula 11, R₆ is an alkylene, and n ranges from 250 to 25,000.

In Formula 12, R₇ to R₁₀ may be the same or different and each isindependently selected from H and alkyls, and n ranges from 120 to12,000. According to one embodiment, each of R₇ to R₁₀ is selected fromH and CH₃.

In Formula 13, R₁₁ and R₁₂ may be the same or different and each isindependently selected from H and alkyls. X₃ and X₄ may be the same ordifferent and each is independently selected from halogens, and n rangesfrom 150 to 10,000. According to one embodiment, X₃ and X₄ are each F.

In Formula 14, R₁₃ and R₁₄ may be the same or different and each isindependently selected from H and alkyls. X₅ to X₁₀ may be the same ordifferent and each is independently selected from halogens, a rangesfrom 120 to 900, and b ranges from 5100 to 5880. According to oneembodiment, R₁₃ and R₁₄ are each H, and X₅ to X₁₀ are each F.

In the formulae of the present invention, the alkyl may be a C₁ to C₇alkyl, or a C₂ to C₄ alkyl. The haloalkyl may be a C₁ to C₇ haloalkyl,or a C₂ to C₄ haloalkyl. The alkylene may be a C₁ to C₇ alkylene, a C₂to C₅ alkylene, a C₂ to C₄ alkylene, or a C₂ to C₃ alkylene.

The negative active material composition may include the negative activematerial in an amount ranging from about 80 to about 95 wt %. Accordingto another embodiment of the present invention, the negative activematerial may be included in an amount ranging from about 90 to about 95wt %. When the negative active material is included in an amount lessthan about 80 wt %, it becomes difficult to fabricate a high capacitynegative electrode. When included in an amount greater than about 95 wt%, there is not enough binder to fabricate an electrode substrate.

In addition, the negative active material composition includes apolyimide precursor compound in an amount ranging from about 4.95 toabout 15 wt %. According to another embodiment, the polyimide precursorcompound is included in an ranging from about 5 to about 7 wt %. Whenthe polyimide precursor compound is included in an amount less thanabout 4.95 wt %, there is not enough binder to fabricate an electrodesubstrate. On the other hand, when the polyimide precursor compound isincluded in an amount greater than 15 wt %, insufficient negative activematerial is included in the negative electrode, making it difficult tofabricate negative electrodes having high capacity.

In addition, the negative active material composition may include ahighly flexible polymer in an amount ranging from about 0.05 to about 10wt %. According to another embodiment, the highly flexible polymer maybe included in an amount ranging from about 0.1 to about 5 wt %.According to still another embodiment, the highly flexible polymer maybe included in an amount ranging from about 0.5 to about 3 wt %. Whenthe highly flexible polymer is included in an amount less than about0.05 wt %, bending of the electrode substrate is difficult to prevent.On the other hand, when the highly flexible polymer is included in anamount greater than about 10 wt %, volume changes in the negative activematerial during repeated charge and discharge are difficult to controldue to the decreased amount of polyimide.

For the conductive agent, any electrically conductive material may beused so long as it does not cause a chemical change. Nonlimitingexamples of suitable conductive agents include natural graphite,artificial graphite, carbon black, acetylene black, ketjen black, carbonfiber, polyphenylene derivatives, and metal powders or metal fibersincluding copper, nickel, aluminum, silver, and so on.

The above negative active material composition is applied on a currentcollector and then dried to form a negative active material layer,thereby fabricating a negative electrode. Polyamic acid, which is apolyimide precursor compound, is converted into polyimide during dryingand exists as polyimide in the negative active material layer. In otherwords, the negative active material layer of the present inventionincludes a negative active material, a polyimide binder, and a highlyflexible polymer.

The polyimide may be produced from a polyimide precursor compoundproduced by a condensation reaction between a first monomer and a secondmonomer. The first monomer may be selected from compounds represented byFormulae 1 to 4, and the second monomer may be selected from compoundsrepresented by Formulae 5 to 9.

The current collector may be selected copper foil, nickel foil,stainless steel foil, titanium foil, nickel foam, copper foam, polymersubstrates coated with a conductive metal, and combinations thereof.

According to another embodiment of the present invention, a rechargeablelithium battery includes the above negative electrode fabricated fromthe negative active material, a positive electrode and a non-aqueouselectrolyte.

The positive electrode includes a positive active material including alithiated intercalation compound that is capable of reversiblyintercalating and deintercalating lithium. Nonlimiting examples ofsuitable lithiated intercalation compounds include composite oxidesincluding lithium and an element selected from cobalt, manganese,nickel, iron, phosphorus, and combinations thereof. The lithiatedintercalation compound may be selected from compounds represented byFormulae 15 to 38.

Li_(a)A_(1-b)B_(b)D₂   Formula 15

In Formula 15, 0.95≦a≦1.1 and 0≦b≦0.5.

Li_(a)E_(1-b)B_(b)O_(2-c)F_(c)   Formula 16

In Formula 16, 0.95≦a≦1.1, 0≦b≦0.5, and 0≦c≦0.05.

LiE_(2-b)B_(b)O_(4-c)F_(c)   formula 17

In Formula 17, 0≦b≦0.5 and 0≦c≦0.05.

Li_(a)Ni_(1-b-c)Co_(b)BcD_(α)  Formula 18

In Formula 18, 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α≦2.

Li_(a)Ni_(1-b-c)Co_(b)B_(c)O_(2-α)F_(α)  Formula 19

In Formula 19, 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2.

Li_(a)Ni_(1-b-c)Co_(b)B_(c)O_(2-α)F₂   Formula 20

In Formula 20, 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2.

Li_(a)Ni_(1-b-c)Mn_(b)B_(c)D_(α)  Formula 21

In Formula 21, 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α≦2.

Li_(a)Ni_(1-b-c)Mn_(b)B_(c)O_(2-α)F_(α)  Formula 22

In Formula 22, 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2.

Li_(a)Ni_(1-b-c)Mn_(b)B_(c)O_(2-α)F₂   Formula 23

In Formula 23, 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2.

Li_(a)Ni_(b)E_(c)G_(d)O₂   Formula 24

In Formula 24, 0.90≦a≦1.1, 0≦b≦0.9, 0≦c≦0.5, and 0.001≦d≦0.1.

Li_(a)Ni_(b)Co_(c)Mn_(d)GeO₂   Formula 25

In Formula 25, 0.90≦a≦1.1, 0≦b≦0.9, 0≦c≦0.5, 0≦d≦0.5, and 0.001≦e≦0.1.

Li_(a)NiG_(b)O₂   Formula 26

In Formula 26, 0.90≦a≦1.1 and 0.001≦b≦0.1.

Li_(a)CoG_(b)O₂   Formula 27

In Formula 27, 0.90≦a≦1.1 and 0.001≦b≦0.1.

Li_(a)MnG_(b)O₂   Formula 28

In Formula 28, 0.90≦a≦1.1 and 0.001≦b≦0.1.

Li_(a)Mn₂G_(b)O₄   Formula 29

In Formula 29, 0.90≦a≦1.1 and 0.001≦b≦0.1.

QO₂   Formula 30

QS₂   Formula 31

LiQS₂   Formula 32

V₂O₅   Formula 33

LiV₂O₅   Formula 34

LiIO₂   Formula 35

LiNiVO₄   Formula 36

Li_(3-f)J₂(PO₄)₃   Formula 37

In Formula 37, 0≦f<3.

Li_(3-f)Fe₂(PO₄)₃   Formula 38

In Formula 38, 0≦f≦2.

In the above formulae, A is selected from Ni, Co, Mn, and combinationsthereof. B is selected from Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rareearth elements, and combinations thereof. D is selected from O, F, S, P,and combinations thereof. E is selected from Co, Mn, and combinationsthereof. F is selected from F, S, P, and combinations thereof. G is atransition element or a lanthanide element selected from Al, Cr, Mn, Fe,Mg, La, Ce, Sr, V, and combinations thereof. Q is a transition elementor a lanthanide element selected from Ti, Mo, Mn, and combinationsthereof. I is a transition element or a lanthanide element selected fromCr, V, Fe, Sc, Y, and combinations thereof. J is a transition element ora lanthanide element selected from V, Cr, Mn, Co, Ni, Cu, andcombinations thereof.

The positive active material may be selected from elemental sulfur (S₈),sulfur-based compounds (such as Li₂S_(n) (n≧1), Li₂S_(n) (n≧1))dissolved in a catholyte, organic sulfur compounds, carbon-sulfurpolymers ((C₂S_(f))_(n): f=2.5 to 50, n≧2), and combinations thereof.

The positive electrode may be fabricated first preparing a positiveactive material composition by mixing a positive active material, abinder, and optionally a conductive agent. The composition is thenapplied on a positive current collector made of a material such asaluminum.

For the conductive agent, any electrically conductive material may beused so long as it does not cause a chemical change. Nonlimitingexamples of suitable conductive agents include natural graphite,artificial graphite, carbon black, acetylene black, ketjen black, carbonfiber, polyphenylene derivatives, and metal powders or metal fibersincluding copper, nickel, aluminum, silver, and so on.

Nonlimiting examples of suitable binders include polyvinyl alcohol,carboxymethyl cellulose, hydroxypropylene cellulose, diacetylenecellulose, polyvinylchloride, polyvinylpyrrolidone,polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, andpolypropylene.

The solvent may be N-methylpyrrolidone, but it is not limited thereto.

The non-aqueous electrolyte includes a non-aqueous organic solvent and alithium salt. The non-aqueous organic solvent acts as a medium fortransmitting ions taking part in the electrochemical reaction of thebattery. The non-aqueous organic solvent may include a carbonate-based,ester-based, ether-based, ketone-based, alcohol-based, or aproticsolvent. Nonlimiting examples of suitable carbonate-based solventsinclude dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropylcarbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate(EPC), methylethyl carbonate (MEC), ethylmethyl carbonate (EMC),ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate(BC), and so on. Nonlimiting examples of suitable ester-based solventsinclude n-methyl acetate, n-ethyl acetate, n-propyl acetate,dimethylacetate, methylpropionate, ethylpropionate, γ-butyrolactone,decanolide, valerolactone, mevalonolactone, caprolactone, and so on.Nonlimiting examples of suitable ether-based solvents include dibutylether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran,tetrahydrofuran, and so on. Nonlimiting examples of suitableketone-based solvents include cyclohexanone and so on. Nonlimitingexamples of suitable alcohol-based solvents include ethanol, isopropylalcohol, and so on. Nonlimiting examples of suitable aprotic solventsinclude nitriles (such as X—CN where X is a C2 to C20 linear, branched,or cyclic hydrocarbon, a double bond, an aromatic ring, or an etherbond), amides (such as dimethylformamide), dioxolanes (such as1,3-dioxolane), sulfolanes, and so on.

The non-aqueous organic solvent may include a single solvent or amixture of solvents. When a mixture of solvents is used, the mixtureratio can be controlled in accordance with the desirable batteryperformance characteristics.

The carbonate-based solvent may include a mixture of cyclic and linearcarbonates. When the cyclic carbonate and linear carbonate are mixed ina volume ratio ranging from about 1:1 to about 1:9, and the mixture isused as an electrolyte, the electrolyte performance may be enhanced.

In addition, according to one embodiment of the present invention, theelectrolyte may further include mixtures of carbonate-based solvents andaromatic hydrocarbon-based solvents. The carbonate-based solvents andthe aromatic hydrocarbon-based solvents are preferably mixed together ina volume ratio ranging from about 1:1 to about 30:1.

The aromatic hydrocarbon-based organic solvent may be represented byFormula 39.

In Formula 39, each of R_(a) to R_(f) is independently selected fromhydrogen, halogens, C1 to C10 alkyls, haloalkyls, and combinationsthereof.

Nonlimiting examples of suitable aromatic hydrocarbon-based organicsolvents include benzene, fluorobenzene, 1,2-difluorobenzene,1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene,1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene,1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene,1,2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene,1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene,1,2,4-triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene,1,3-difluorotoluene, 1,4-difluorotoluene, 1,2,3-trifluorotoluene,1,2,4-trifluorotoluene, chlorotoluene, 1,2-dichlorotoluene,1,3-dichlorotoluene, 1,4-dichlorotoluene, 1,2,3-trichlorotoluene,1,2,4-trichlorotoluene, iodotoluene, 1,2-diiodotoluene,1,3-diiodotoluene, 1,4-diiodotoluene, 1,2,3-triiodotoluene,1,2,4-triiodotoluene, xylene, and combinations thereof.

The electrolyte may further include an additive such as vinylenecarbonate or fluoroethylene carbonate to improve cycle-lifecharacteristics. The additive may be used in an appropriate amount.

The lithium salt is dissolved in the non-aqueous organic solvent tosupply lithium ions in the battery. It enables the basic operation ofthe rechargeable lithium battery, and facilitates transmission oflithium ions between the positive and negative electrodes. Nonlimitingexamples of suitable lithium salts include supporting electrolyte saltsselected from LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiCF₃SO₃, LiN(SO₂C₂F₅)₂,LiN(CF₃SO₂)₂, LiC₄F₉SO₃, LiCIO₄, LiAlO₄, LiAlCl₄,LiN(C_(x)F_(2x+1)SO₂)(C_(y)F_(2y+1)SO₂) (where x and y are naturalnumbers), LiCl, LiI, lithium bisoxalate borate, and combinationsthereof.

The lithium salt may be used at a concentration ranging from about 0.1to about 2.0M. When the lithium salt concentration is less than about0.1M, electrolyte performance may deteriorate due to low electrolyteconductivity. When the lithium salt concentration is greater than about2.0M, lithium ion mobility may be reduced due to increased electrolyteviscosity.

In addition, nonlimiting examples of suitable solid electrolytes includepolyethylene oxide polymer electrolytes, polymer electrolytes includingat least one polyorganosiloxane or polyoxyalkylene side chain, sulfideelectrolytes (such as Li₂S—SiS₂, Li₂S—GeS₂, Li₂S—P₂S₅, Li₂S—B₂S₃, andthe like), and inorganic electrolytes such as Li₂S—SiS₂—Li₃PO₄,Li₂S—SiS₂—Li₃SO₄, and the like.

The rechargeable lithium battery generally includes a separator betweenthe positive electrode and the negative electrode. Nonlimiting examplesof suitable separators include polyethylene, polypropylene, andpolyvinylidene fluoride, and multilayers thereof (such aspolyethylene/polypropylene bilayered separators,polyethylene/polypropylene/polyethylene three-layered separators, andpolypropylene/polyethylene/polypropylene three-layered separators).

FIG. 2 illustrates a rechargeable lithium battery having theabove-mentioned structure according to one embodiment of the presentinvention. As shown in FIG. 2, a cylindrical lithium ion cell 100includes a negative electrode 102, a positive electrode 103, a separator104 between the negative electrode 102 and the positive electrode 103,an electrolyte impregnating the separator 104, a battery case 105, and asealing member 106 sealing the battery case 105. The rechargeablelithium battery according to the present embodiment is not limited tothe above-mentioned shape, and may be shaped into a prismatic shape, apouch, and so on.

The following examples illustrate certain embodiments of the presentinvention. These examples are presented for illustrative purposes onlyand are not intended to limit the scope of the present invention.

EXAMPLE 1

9.5 wt % of a polyamic acid, 85 wt % of a silicon negative activematerial, 0.5 wt % of a polyvinylidenefluoride highly flexible polymer,and 5 wt % of a carbon black conductive agent were mixed in anN-methylpyrrolidone solvent to prepare a negative active materialslurry. The negative active material slurry was coated on a coppercurrent collector and dried at 120° C. to prepare a negative electrode.The negative electrode was loaded at 2.7 mg/cm². Accordingly, thenegative electrode included a negative active material layer including apolyimide binder, which was horizontally coated on a flat copper currentcollector.

EXAMPLE 2

A negative electrode was prepared as in Example 1, except that anegative active material layer was loaded at 3.9 mg/cm².

EXAMPLE 3

A negative electrode was prepared as in Example 1, except that anegative active material layer was loaded at 4.2 mg/cm².

EXAMPLE 4

A negative electrode was prepared as in Example 2, except thatpolyvinylidenefluoride was replaced with polyvinylacetate.

EXAMPLE 5

A negative electrode was prepared as in Example 3, except thatpolyvinylidenefluoride was replaced with apolyvinylidenefluoride-hexafluoropropylene copolymer.

EXAMPLE 6

A negative electrode was prepared as in Example 2, except thatpolyvinylidenefluoride was replaced with polyethyleneoxide.

EXAMPLE 7

A negative electrode was prepared as in Example 1, except thatpolyvinylidenefluoride was included in an amount of 0.1 wt %.

EXAMPLE 8

A negative electrode was prepared as in Example 1, except thatpolyvinylidenefluoride was included in an amount of 0.3 wt %.

EXAMPLE 9

A negative electrode was prepared as in Example 1, except thatpolyvinylidenefluoride was included in an amount of 3 wt %.

EXAMPLE 10

A negative electrode was prepared as in Example 1, except thatpolyvinylidenefluoride was included in an amount of 7 wt %.

EXAMPLE 11

A negative electrode was prepared as in Example 1, except thatpolyvinylidenefluoride was included in an amount of 10 wt %.

COMPARATIVE EXAMPLE 1

10 wt % of a polyamic acid, 85 wt % of a silicon negative activematerial, and 5 wt % of a carbon black conductive agent were mixed in anN-methylpyrrolidone solvent to prepare a negative active materialslurry. The negative active material slurry was coated on a coppercurrent collector and dried at 120° C. to prepare a negative electrode.The negative electrode was loaded at 2.7 mg/cm².

COMPARATIVE EXAMPLE 2

A negative electrode was prepared as in Comparative Example 1, exceptthat the loading amount was 3.9 mg/cm².

COMPARATIVE EXAMPLE 3

A negative electrode was prepared as in Comparative Example 1, exceptthat the loading amount was 4.2 mg/cm².

Photographs of a Bent Negative Electrode Depending on Loading Amounts

The negative electrodes prepared according to Examples 1 to 3 arerespectively shown in FIGS. 3, 4, and 5.

FIGS. 6, 7, and 8 are photographs of the negative electrodes preparedaccording to Comparative Examples 1 to 3.

As shown in FIGS. 3 to 5, the negative electrodes having negative activematerial layers including a highly flexible polymer were not bentregardless of the amount of negative active material slurry loaded onthe copper current collector.

On the contrary, as shown in FIGS. 6 to 8, the negative electrodeshaving negative active materials not including a highly flexible polymerwere more severely bent as the amount of negative active material slurryloaded on the copper current collector increased.

Result of Capacity and Cycle-Life Characteristics

18650-type cylindrical batteries having diameters of 18 mm and heightsof 65 mm were fabricated using the negative electrodes preparedaccording to Examples 1 to 3 and Comparative Examples 1 to 3, a positiveelectrode including a lithium cobalt oxide positive active material, andan electrolyte prepared by dissolving 1M of LiPF₆ in an organic solventincluding a mixture of ethylenecarbonate and diethylcarbonate in avolume ratio of 3:7. The cylindrical batteries were charged anddischarged for 100 cycles at a 0.5 C rate. Their discharge capacityretentions at 10 cycles, 50 cycles, and 100 cycles are shown in Table 1.

TABLE 1 Discharge Capacity Retention (%) 10 cycles 50 cycles 100 cyclesExample 1 91.0% 85.3% 80.2% Example 2 89.8% 83.9% 77.5% Example 3 88.0%81.4% 74.8% Comparative Example 1 87.5% 81.7% 74.5% Comparative Example2 The substrates were bent so that Comparative Example 3 substratescoated on both sides could not be made. Therefore, cells were notfabricated.

As shown in Table 1, the battery prepared with the negative activematerial composition of Example 3 (loaded at 4.2 mg/cm²) turned out tohave a similar capacity retention to that of the battery prepared withthe negative active material composition of Comparative Example 1(loaded at 2.7 mg/cm² and not including the highly flexible polymer)even at the 100^(th) cycle. Therefore, the battery including thenegative active material composition of Example 3 maintains capacityretention even if the negative active material is increasingly loaded.Accordingly, the battery including the negative active materialcomposition of Example 3 has high capacity.

Therefore, the inventive negative active material compositions forrechargeable lithium batteries can prevent electrode substrates frombending and provide the substrates with flexibility, thereby improvingcapacity and cycle-life characteristics of the batteries.

While the present invention has been illustrated and described withreference to certain exemplary embodiments, it will be understood bythose of ordinary skill in the art that various changes andmodifications may be made to the described embodiments without departingfrom the spirit and scope of the present invention as defined by thefollowing claims.

1. A negative active material composition for a rechargeable lithiumbattery, comprising: a negative active material; a polyimide precursorcompound; and a flexible polymer.
 2. The negative active materialcomposition of claim 1, wherein the negative active material is selectedfrom the group consisting of lithium metal, lithium alloys, materialscapable of reacting with lithium to form lithium-containing compounds,and materials capable of reversibly intercalating and deintercalatinglithium ions.
 3. The negative active material composition of claim 2,wherein the lithium alloy comprises an alloy of lithium and a metalselected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr,Ba, Ra, Al, Sn, and combinations thereof.
 4. The negative activematerial composition of claim 2, wherein the material capable ofreacting with lithium is selected from the group consisting of SnO,SnO₂, titanium nitrates, SiO, SiO_(x) wherein 0<x<2, silicon, andcombinations thereof.
 5. The negative active material composition ofclaim 2, wherein the material capable of reversibly intercalating anddeintercalating lithium ions is a carbon-based material.
 6. The negativeactive material composition of claim 1, wherein the polyimide precursorcompound comprises a reaction product of a condensation reaction of afirst monomer and a second monomer, wherein the first monomer isselected from the group consisting of compounds represented by Formulae1 to 4 and wherein the second monomer is selected from the groupconsisting of compounds represented by Formulae 5 to 9:

wherein: each of X₁ and X₂ is independently selected from the groupconsisting of O, CO, SO₂, and S; each of R₁ and R₂ is independentlyselected from the group consisting of H and alkyls; each of R₃ and R₄ isindependently selected from the group consisting of halogens,haloalkyls, alkyls, and combinations thereof.
 7. The negative activematerial composition of claim 6, wherein each of R₃ and R₄ is ahaloalkyl.
 8. The negative active material composition of claim 1,wherein the flexible polymer has a glass transition temperature of lessthan about 50° C.
 9. The negative active material composition of claim1, wherein the flexible polymer has a weight average molecular weightranging from about 10,000 to about 1,000,000.
 10. The negative activematerial composition of claim 1, wherein the flexible polymer isselected from the group consisting of compounds represented by Formulae10 to 14 and combinations thereof:

wherein R₅ is an alkylene, and n ranges from 120 to 1000;R₆—O_(n)   Formula 11 wherein R₆ is an alkylene, and n ranges from 250to 25,000;

wherein each of R₇ to R₁₀ is independently selected from the groupconsisting of H and alkyls, and n ranges from 120 to 12,000;

wherein each of R₁₁ and R₁₂ is independently selected from the groupconsisting of H and alkyls, wherein each of X₃ and X₄ is a halogen, andn ranges from 150 to 10,000; and

wherein each of R₁₃ and R₁₄ is independently selected from the groupconsisting of H and alkyls, wherein each of X₅ to X₁₀ is a halogen,wherein a ranges from 120 to 900, and b ranges from 5100 to
 5880. 11.The negative active material composition of claim 1, wherein theflexible polymer is selected from the group consisting of polypropylenecarbonate, polyethylene oxide, polypropylene oxide, polyvinylacetate,polyvinylidenefluoride, a polyvinylidenefluoride-hexafluoropropylenecopolymer, and combinations thereof.
 12. The negative active materialcomposition of claim 1, wherein the flexible polymer is present in anamount ranging from about 0.05 to about 10 wt %.
 13. A negativeelectrode comprising: a current collector; and a negative activematerial layer on the current collector, the negative active materiallayer comprising a negative active material, a polyimide binder, and aflexible polymer.
 14. The negative electrode of claim 13, wherein thepolyimide binder comprises a reaction product of a dehydration reactionof a polyimide precursor compound, wherein the polyimide precursorcompound comprises a reaction product of a condensation reaction of afirst monomer and a second monomer, wherein the first monomer isselected from the group consisting of compounds represented by Formulae1 to 4, and wherein the second monomer is selected from the groupconsisting of compounds represented by Formulae 5 to 9:

wherein: each of X₁ and X₂ is independently selected from the groupconsisting of O, CO, SO₂, and S; each of R₁ and R₂ is independentlyselected from the group consisting of H and alkyls; and each of R₃ andR₄ is independently selected from the group consisting of halogens,haloalkyls, alkyls, and combinations thereof.
 15. The negative electrodeof claim 13, wherein the flexible polymer has a glass transitiontemperature of less than about 50° C.
 16. The negative electrode ofclaim 13, wherein the flexible polymer has a weight average molecularweight ranging from about 10,000 to about 1,000,000.
 17. The negativeelectrode of claim 13, wherein the flexible polymer is selected from thegroup consisting of compounds represented by Formulae 10 to 14 andcombinations thereof:

wherein R₅ is an alkylene, and n ranges from about 120 to 1000;R₆—O_(n)   Formula 11 wherein R₆ is an alkylene, and n ranges fromabout 250 to 25,000;

wherein each of R₇ to R₁₀ is selected from the group consisting of H andalkyls, and n ranges from 120 to 12,000;

wherein each of R₁₁ and R₁₂ is independently selected from the groupconsisting of H and alkyls, wherein each of X₃ and X₄ is a halogen, andn ranges from 150 to 10,000; and

wherein each of R₁₃ and R₁₄ is independently selected from the groupconsisting of H and alkyls, wherein each of X₅ to X₁₀ is a halogen, aranges from 120 to 900, and b ranges from 5100 to
 5880. 18. The negativeelectrode of claim 13, wherein the flexible polymer is selected from thegroup consisting of polypropylene carbonate, polyethylene oxide,polypropylene oxide, polyvinylacetate, polyvinylidenefluoride, apolyvinylidenefluoride-hexafluoropropylene copolymer, and combinationsthereof.
 19. A rechargeable lithium battery comprising: a negativeelectrode comprising a negative active material layer on a currentcollector, the negative active material layer comprising a negativeactive material, a polyimide binder, and a flexible polymer; and apositive electrode comprising a positive active material capable ofreversibly intercalating and deintercalating lithium ions.
 20. Therechargeable lithium battery of claim 19, wherein the polyimide bindercomprises a reaction product of a dehydration reaction of a polyimideprecursor compound, wherein the polyimide precursor compound comprises areaction product of a condensation reaction of a first monomer and asecond monomer, wherein the first monomer is selected from the groupconsisting of compounds represented by Formulae 1 to 4, and wherein thesecond monomer is selected from the group consisting of compoundsrepresented by Formulae 5 to 9:

wherein: each of X₁ and X₂ is independently selected from the groupconsisting of O, CO, SO₂, and S; each of R₁ and R₂ is independentlyselected from the group consisting of H and alkyls; and each of R₃ andR₄ is independently selected from the group consisting of halogens,haloalkyls, alkyls, and combinations thereof.
 21. The rechargeablelithium battery of claim 19, wherein the flexible polymer has a glasstransition temperature of less than about 50° C.
 22. The rechargeablelithium battery of claim 19, wherein the flexible polymer has a weightaverage molecular weight ranging from about 10,000 to 1,000,000.
 23. Therechargeable lithium battery of claim 19, wherein the flexible polymeris selected from the group consisting of compounds represented byFormulae 10 to 14 and combinations thereof:

wherein R₅ is an alkylene, and n ranges from 120 to 1000;R₆—O_(n)   Formula 11 wherein R₆ is an alkylene, n ranges from 250 to25,000;

wherein each of R₇ to R₁₀ is independently selected from the groupconsisting of H and alkyls, and n ranges from 120 to 12,000;

wherein each of R₁₁ and R₁₂ is independently selected from the groupconsisting of H and alkyls, wherein each of X₃ and X₄ is a halogen, andn ranges from 150 to 10,000; and

wherein each of R₁₃ and R₁₄ is independently selected from the groupconsisting of H and alkyls, each of X₅ to X₁₀ is a halogen, and whereina ranges from 120 to 900, and b ranges from 5100 to
 5880. 24. Therechargeable lithium battery of claim 19, wherein the flexible polymeris selected from the group consisting of polypropylene carbonate,polyethylene oxide, polypropylene oxide, polyvinylacetate,polyvinylidenefluoride, a polyvinylidenefluoride-hexafluoropropylenecopolymer, and combinations thereof.